Progress in electrocatalytic nitrate reduction for green energy:Catalyst engineering,mechanisms,and techno-economic feasibility

Ammonia(NH_(3))is an irreplaceable chemical that has been widely demanded to keep the sustainable development of modern society.However,its industrial production consumes a huge amount of energy and releases extraordinary greenhouse gases(GHGs),leading to various environmental issues.Achieving the green production of ammonia is a great challenge,which has been extensively pursued in the last decade.In this review,the most promising strategy,electrochemical nitrate reduction reaction(e-NO_(3)RR),is comprehensively investigated to give a complete understanding of its development and mechanism and provide guidance for future directions.However,owing to the complex reactions and limited selectivity,a comprehensive understanding of the mechanisms is crucial to further development and commercialization.Moreover,NO_(3)^(-)RR is a promising strategy for simultaneous water treatment and NH_(3)production.A detailed overview of the recent progress in NO_(3)^(-)RR for NH_(3)production with nontransition and transition metal based electrocatalysts is summarized.In addition,critical advanced techniques,future challenges,and prospects are discussed to guide future research on transition metal-based catalysts for commercial NH_(3)synthesis by NO_(3)^(-)reduction.

Contribution of phytoliths to total biogenic silica volumes in the tropical rivers of Malaysia and associated implications for the marine biogeochemical cycle

The contribution of phytoliths to total biogenic silica(BSi) volumes in rivers worldwide,and the associated implications for the biogeochemical cycle,require in-depth study.Based on samples from rivers in Peninsular Malaysia,this project investigated the source and characteristics of B Si found in Asian tropical rivers,as well as the process of reverse weathering taking place in these fluvial systems.Results indicated that BSi samples collected in sediments consisted of phytolith,diatom and sponge spicules.Phytoliths,predominantly of the elongate form,comprised 92.8%-98.3% of BSi in the Pahang River.Diatom BSi in this river consisted mainly of pennatae diatoms,but represented a relatively small proportion of the total BSi volume.However,diatom BSi(predominantly of the Centricae form) was more prevalent in the Pontian and Endau Rivers with shares of 68.8% and 79.3% of the total BSi volumes,respectively,than Pahang River.Carbon contents of the BSi particulates ranged from 1.85% to 10.8% with an average of 4.79%.These values are higher than those recorded in other studies to date,and indicate that BSi plays a major role in controlling permanent carbon burial.This study suggests that phytoliths from terrestrial plants are the primary constituents of BSi in the rivers of Peninsular Malaysia,and therefore represent a significant proportion of the coastal silica budget.

Density functional theory study of CO catalytic oxidation on Co_2B_2/TiO_2(110) surface

Titanium dioxide with CoB amorphous alloys nanoparticles deposited on the surface is known to exhibit higher catalytic activity than the CoB amorphous.A study of the structure of such system is necessary to understand this effect.A quantum chemical study of Co2B2 on the TiO2（110） surface was studied using periodic slab model within the framework of density functional theory（DFT）.The results of geometry optimization indicated that the most stable model of adsorption was Co2B2 cluster adsorbed on the hollow site of TiO2 .The adsorption energy calculated for Co2B2 on the hollow site was 439.3 kJ/mol.The adsorption of CO and O2 was further studied and the results indicated that CO and O2 are preferred to adsorb on the Co2 site.Co-adsorption of CO and O2 shows that Co2B2 /TiO2 is a good catalyst for the oxidation of CO to carbon dioxide in the presence of oxygen.

Surface-enhanced Raman scattering properties of highly ordered self-assemblies of gold nanorods with different aspect ratios

Gold nanorods with aspect ratios of from 1 （particles） to 31.6 were synthesized by the seed-mediated method and packed in a highly ordered structure on a large scale on silicon substrates through capillary force induced self-assembly behaviour during solvent evaporation. The gold nanorod surface exhibits a strong enhancing effect on Raman scattering spectroscopy. The enhancement of Raman scattering for two model molecules （2-naphthalenethiol and rhodamine 6C） is about 5-6 orders of magnitude. By changing the aspect ratio of the Au nanorods, we found that the enhancement factors decreased with the increase of aspect ratios. The observed Raman scattering enhancement is strong and should be ascribed to the surface plasmon coupling between closely packed nanorods, which may result in huge local electromagnetic field enhancements in those confined junctions.

Antitumor and immune regulation activities of the extracts of some Chinese marine invertebrates

Extracts of 21 marine invertebrates belonging to Coelenterata, Mollusca, Annelida, Bryozoa, Echiura, Arthropoda, Echinodermata and Urochordata were screened for the studies on their antitumor and immune regulation activities. Antitumor activity was determined by MTT method and immune regulation activity was studied using T- and B-lymphocytes in mice spleen in vitro. It was found that the n-butanol part of Asterina pectinifera, the acetic ether part of Tubuaria marina,95% ethanol extract of Acanthochiton rubrolineatus have a high inhibition rate of 96.7%,63.9% and 50.5% respectively on tumor cell line HL-60 at the concentration of 0.063 mg/ml. The inhibition rate of the acetic ether part of Tubuaria marina on the tumor cell line A-549 is 65.4 % at concentration of 0.063 mg/mL. The 95% ethanol extract of Meretrix meretrix has so outstanding promoting effect on T-lymphocytes that their multiplication increases 25% when the sample concentration is only 1 μg/ml. On B-lymphocytes, the 95% extract of Rapana venosa, at concentration of 100 μg/ml, has a promotion percent- age of 60%. On the other hand, under the condition of no cytotoxic effect, the 95% ethanol extracts of Acantho- chiton rubrolineatus and Cellana toreum can reach 92% inhibition rate on T lymphocyte at concentration of 100 μg/ml, while the inhibition rate on B lymphocyte of the 95% extract of Acanthochiton rubrolineatus reaches 92% at the same concentration.

Synthesis and Properties of Dendritic Long-Chain Esters as Crude Oil Flow Improver Additives

The efficiencies of 6 kinds of macromolecules with dendritic structure in improving the flow properties of crude oil were investigated. The dendritic additives were synthesized using low-generation dendritic poly(amidoamine) and alkyl longchain acrylic esters as starting materials, and their structures were characterized by the Fourier transform infrared spectroscopy, 1H-nuclear magnetic resonance and elemental analysis. The effects on the pour point and rheological properties of crude oil samples were studied. Efficiencies of dendritic long-chain esters were not only influenced by the alky chain length, but also by the generation of dendrimer. The longer the alkyl chain of dendritic long-chain ester was, the better the effect in the reduction of pour point and apparent viscosity was. Efficiencies of 1.5 generation dendritic long-chain ester with 8 branched chains for the reduction of pour point and apparent viscosity were superior to those of 0.5 generation dendritic long-chain ester with 4 branched chains. Under the same conditions, efficiencies of 1.5 generation dendritic eighteen ester were superior to those of other 1.5 generation dendritic long-chain esters for the reduction of pour point and viscosity of crude oil.

Synthesis and Crystal Structure of a New Mo/Au/S Cluster [Et_4N][Mo_2S_4(AuPPh_3)(edt)_2]· 0.25Et_2O·0.25MeOH(edt=Ethanedithiolate)

Reactions of the preformed cluster precursor [Et4N]2[Mo2S2（μ-S）2（edt）2] （edt = ethanedithiolate） （1） with [Au（PPh3）Cl] in MeOH/MeCN gave rise to a new heterobimetallic Mo/Au/S cluster [Et4N][Mo2S4（AuPPh3）（edt）2]·0.25Et2O·0.25MeOH （2·0.25Et2O·0.25MeOH）. It was characterized by elemental analysis, IR spectrum and X-ray analysis. 2·0.25Et2O·0.25MeOH crystallizes in the monoclinic system, space group C2/c with a = 20.117（4）, b = 9.2705（19）, c = 44.418（9） A^°, β= 93.19（3）°, V = 8271（3） A^°^3, Z = 8, Dc = 1.794 g/cm^3, T = 193 K, C31.25H43AuMo2NO0.50PS8, Mr = 1116.96, F（000） = 4380, μ（MoKa） = 4.603 mm^-1, S = 1.019, R = 0.0672 and wR = 0.1708 for 7243 observed reflections with I 〉 2σ（I）. The anion of 2 consists of a butterfly-shaped Mo2S4Au core in which one [AuPPh3]^＋ cation is coordinated by one bridging S and two terminal S atoms of the [（edt）2Mo2（S）2（μ-S）2] moiety. The Au（I） center adopts a pseudo-tetrahedral coordination geometry, and the Au-S bond lengths vary from 2.425（2） to 2.898（3）A^°.

Synthesis and Crystal Structure of an Ionic Compound [Fe(CN)_6·(PhCH_2NC_9H_7)_4]·12H_2O

A novel ionic compound [Fe（CN）6·（PhCHeNC9H7）4]·12H2O（C70H80FeN10O12, Mr = 1309.29） has been synthesized and its structure was characterized by I-R, elemental analysis and X-ray diffraction. The compound crystaUizes in triclinic, space group P1, with a = 10.968（7）, b = 11.466（7）, c = 14.077（8）A, α= 87.014（7）, β= 78.124（7）, γ = 72.708（7）°, V = 1654.1（17）A3, Z = 1, Dc = 1.314 g·cm^-3, F（000） = 692, p = 0.298 mm^-1, the final R = 0.0519 and wR = 0.1355. The building unit of the title compound consists of four （PhCH2N＋C9H7） ions, one [Fe（CN）6]4- anion, and a dozen water molecules. According to the structural analysis, [Fe（CN）6]4- ions are linked together by O-H…O and O-H…N hydrogen bonds, while （PhCH2N＋C9HT） and [Fe（CN）6]4- ions interact with each other by electrostatic force to form an ionic compound.

Esterification of Free Fatty Acids in Waste Cooking Oil by Heterogeneous Catalysts

Waste cooking oil(WCO) is becoming the most promising alternative feedstock to produce biodiesel due to its low cost in China. In this study, NKC-9 ion-exchange resin and H-beta zeolite were selected as heterogeneous catalysts in the WCO esterification process and their esterification characteristics were compared by orthogonal experiments. NKC-9 resin showed higher activity and achieved a higher final conversion compared with H-beta zeolite under the same reaction conditions. Reusability experiments showed that NKC-9 resin still exhibited high activity after 5 runs. The effects of the mole ratio of alcohol to oil, reaction time, reaction temperature and the catalyst dose were investigated by multifactor orthogonal analysis. The influence of the free fatty acid(FFA) content was also investigated, and the result showed that the esterification rate could be as high as 98.4% when the FFA content was 6.3wt%.

Electrospun P(LLA-CL) Nanofibers Loaded with Vitamins E TPGS as Antibacterial Wound Dressing Materials

To obtain the wound dressings which can accelerate healing effectively,vitamin E D-α-Tocopherol polyethylene glycol succinate(vitamin E TPGS),one of the common derivatives of the unstable vitamins E,was successfully incorporated into P(LLA-CL)nanofibers by electrospinning.Electron microscopy showed that the smooth cylindrical fibers were obtained,albeit with a small amount of beading visible for the vitamins-loaded fibers.The diameters of the P(LLA-CL)fibers decreased with the addition of vitamins.The incorporation of the vitamin E TPGS in the electrospun fibers was confirmed by Fourier transform infrared spectroscopy(FTIR).Moreover,X-ray diffraction(XRD)indicated that vitamin E TPGS existed in the amorphous physical form after electrospinning.Fibers containing vitamin E TPGS showed a sustained release profile over more than 100 h in vitro.Antibacterial tests demonstrated that fibers loaded with vitamin E TPGS were effective in inhibiting the growth of E.coli and S.aureus.MTT assay showed that the fibers could promote the proliferation of L929 fibroblasts.These results above demonstrate the potential of P(LLA-CL)/vitamins E TPGS(P/E)as advanced wound dressing materials.

Synthesis of High Surface Area and Well Crystallized Mesoporous WC at Low Temperature with a Pore Structure Collapsed Replication Route

An approach named ＂pore structure collapsed replication route＂ has been developed to prepare mesoporous WC materials with a high surface area （105 m2/g） and crystallized framework at a temperature as low as 700 ℃. The XRD, TEM, EDS, and BET characterizations were conducted to analyze the effects of the synthesis parameters and the template types on the structure of mesoporous WC. The compaction on the templates is the key to form mesoporous structure of WC while the templates help to control the size of crystalline. At a content of 7 wt% for the precursor of WC, the mesoporous WC could be formed with well ordered structure.

Adsorption of Cu^(2+), Zn^(2+) and Cd^(2+) on Bacillus subtilis

A process of biosorption of Cu^2＋, Zn^2＋ and Cd^2＋ on Bacillus subtilis was investigated. The experiments show that the process of biosorption is quite fast, The maximum adsorption was reached after 5 min and hardly changed with time. The experimental data was analyzed using four sorption kinetic models： the pseudo-first-order, the Ritchie second-order, the modified second-order and the Elovich equations, which helped to determine the best-fit equation for the sorption of metal ions onto biomass, The results show that both the Ritchie second-order and modified secondorder equations can fit the experimental data. The Langmuir model is able to accurately describe adsorption of Cu^2＋ and Zn^2＋ on B. subtilis. The experimental data points of adsorption Cd^2＋ and Zn^2＋ on B. subtilis are described by Freundlich isotherms model.

A New Method for the Non-destructive Determination of Fish Freshness by Nuclear Imaging

A new method for determining the freshness of harvested carp using nuclear imaging technology is presented.This research attempted to determine the freshness of carp by measuring the radioactive area increase (RAI) value of fish.The carp samples were maintained under refrigerated condition for 12d, and RAI and total volatile base nitrogen (T-VBN)values were determined during the storage. The results showed that the RAI value increased with the T-VBN content duringthe storage. Also, there is a significant correlation between T-VBN content and RAI value of the carp kept in refrigeratedcondition. The results of this study suggest that the RAI value could be utilized to evaluate rapidly the freshness of carp.

Ecological Costs Applied in the Bleaching of Cotton： A Study for an Optimized Process

The aim of this paper was to study three variables in hydrogen peroxide bleaching of cotton fabrics： the amount of hydrogen peroxide （H2O2）, peroxide stabilizer （Na2SiO3） and the process temperature. The factorial planning of two levels and three factors was done in order to obtain an optimized recipe for subsequent comparison with commons recipes used in industry. Were evaluated the brightness （DL）, energy consumption （dQ）, H2O2 residual （Rox）, processing time and ecological costs.

The New Detection and the Basic Characteristics of the Structural System of Taiwan Region of China—Using the Earth Satellite's Remote-sensing Images to Explain the Structural System of Taiwan Region of China

This text uses the regional geological investigation data and the remote sensing image data of earth-satellite remote sensing to synthetically analyze the structural system of Taiwan region of China. Authors detection-marked and assurance-marked and divided 5 kinds of structural system of the Taiwan region: (1) the wreath-shaped structural system, (2) the N-N-E oriented structural system, (3) the S-N oriented structural system, (4) the N-E oriented structural system, (5) the arc-shaped structural system. Combination of the texture faces and associated method were adopted to recover and reconstruct the structural evolution sequences and the formation periods. In this paper, problems such as the development process in geology etc. are also discussed, contributing new information to research the structural field of the East Asia and its tectonic plate movements and structural actions inside the land plate .

Two New Bisabolane Sesquiterpenes from Leontopodium longifolium

Two new bisabolane sesquiterpenes were isolated from the roots of Leontoptdium longifolium. Their structures were elucidated as 4α, 5α-diacetoxy-lα-angeloyloxybisabol-2, 9, ll-triene and 4α, 5α-diacetoxy-lα-angeloyloxy-ll-hydroxybisabol-2, 9-diene by spectroscopic methods including the 2D NMR techniques.

Two New Oplopanol Esters from Ligularia narynensis

Tow new oplopanol esters were isolated from the roots of Ligularia narynensis. Their structures were eluc idated by spectroscopic methods, especially 2D-NMR techniques.

Biopolymer passivation for high-performance perovskite solar cells by blade coating

Thin films of perovskite deposited from solution inevitably introduce large number of defects,which serve as recombination centers and are detrimental for solar cell performance.Although many small molecules and polymers have been delicately designed to migrate defects of perovskite films,exploiting credible passivation agents based on natural materials would offer an alternative approach.Here,an ecofriendly and cost-effective biomaterial,ploy-L-lysine(PLL),is identified to effectively passivate the defects of perovskite films prepared by blade-coating.It is found that incorporation of a small amount(2.5 mg mL^(-1))of PLL significantly boosts the performance of printed devices,yielding a high efficiency of 19.45% with an increase in open-circuit voltage by up to 100 mV.Density functional theory calculations combined with X-ray photoelectron spectroscopy reveal that the functional groups(-NH2,-COOH)of PLL effectively migrate the Pb-I antisite defects via Pb-N coordination and suppress the formation of metallic Pb in the blade-coated perovskite film.This work suggests a viable avenue to exploit passivation agents from natural materials for preparation of high-quality perovskite layers for optoelectronic applications.

A Novel Method to Produce Quantum Dots

A novel method to produce quantum dots on Si substrate using AAO template and UV pulsed laser deposition technique was proposed and tested.AAO template fabricated by two-step method was put in front of si single crystal substrate.The luminescence target material La_(0.95)Eu_(0.05)BaB_(9)O_(16)was ablated by pulsed UV laser(248nm),and passed through the holes in AAO template,and was deposited on the substrate.Both Raman and luminescence spectra were measured to find the difference between the bulk target and the dots materials.

A review on the rational design and fabrication of nanosized highentropy materials

High-entropy materials are mainly composed of high-entropy alloys(HEAs)and their derivates.Among them,HEAs account for a big part.As a new kind of alloy,they are now arousing great interests because of their high mechanical strength,extraordinary fracture toughness,corrosion resistance compared with traditional alloys.These characteristics allow the use of HEAs in various fields,including mechanical manufacturing,heat-resistant,radiation-resistant,corrosion-resistant,wear-resistant coatings,energy storage,heterocatalysis,etc.In order to promote the extensive application of HEAs,it is of significance to realize their rational design and preparation.In this paper,a systematic review focusing on the rational design and fabrication of nanosized HEAs is given.The design principles of how to match different elements in HEAs and the premise for the formation of single-phase solid solution HEAs are first illustrated.Computation methods for the prediction of formation conditions and properties of HEAs are also in discussion.Then,a detailed description and comparison of the synthesis methods of HEAs and their derivate,as well as their growing mechanism under various synthetic environments is provided.The commonly used characterization methods for the detection of HEAs,along with the typical cases of the application of HEAs in industrial materials,energy storage materials and catalytic materials are also included.Finally,the challenges and perspectives in the design and synthesis of HEAs would be proposed.We hope this review will give guidance for the future development of HEAs materials.